Solvent or plasticizer for compositions with cellulose derivatives



I nns invention relates tov the: manufacture of" Patented Dec. 18, 1 934 UNITED STATES SOLVENT 0R r ASTICIZER FOR COMPOSI- TION S WITH CELLULOSE DERIVATIVES a I Leonard NicholL Nyack, N. Y., assignor to Kay- Fries Chemicals,

Inc; West Haverstraw, N. Y.; v a cornoration ol' New York ,NouDrawin gr Application December 6, 1932, '1

Se ialNo. 645,949 I f1'4 Claims (01.106-40) solutions, films, lacquers, enamels, plastics, coatings or other compositions, preparations or arti-" cles made with derivatives of cellulose;

tives; or in some situations without such volatile solvents, higher boiling solvents,' called plas- -ticize rs, 'areemployedior .the cellulose deriva-: tive or derivatives forming the basisof the com- By the? term,plasticizeris, therepositions. 'fore, meant herein a material imparting flexibility tofilms comprising derivatives of cellulose, such was cellulose acetate, and of such low volatility that such material will remain fora long period of time as a constituent of thefilm or coating of which it originally forms a :part.';1-'I"he.choice of plasticizers has heretofore been confined to relativelyfew of the available substances and all of these have, one ,or more undesirable characteris-; the composition tics 101 fall short 'of affording to: the maximum of desired qualities.

-.0ne object ofthelpresent invention is {65151 vide a plasticizer: for compositions with cellulose" derivatives which can be used forvmany'purposes,

such as -lacquers,-,films,;enamels; plastics, coating fabrics and the like. I I

.n The invention also videcompositions with cellulose derivatives pro-. ducing films havinggreater-durability and pliability, 1

. It is also an object of invention to provide a plasticizer-which shall produce an improved compo t on w th ce u e de at ve Itis also an objectof the invention to provide a plasticizer for cellulose derivatives having a methyl or methylene ether group and manifesting an increased solvent power thereby increasing the and whereby films made therefrom shall have greater flexibility and other desirable properties in increased degrees. v 1

'These objects are accomplished broadly 'by using as plasticizers for cellulose estersand acetates an ester comprising a methylene ether groupjj LThese' esters have exceptional solvent properties, are non exuding and impart to" the cellulose 1 derivative 'fllms containing them, greater pliability and wearing qualities. Of the variousesters that maybe used, particular mentionis made of esters or ester compoundsof polybasic' acldsbcontainingat least one methylene glycol group and especially such as have meth-- J ylene glycol mono ethers in place ofianiordi- In addition to the volatile'solvents or diluents generally used in making solutions (hereinafter referred to as compositions) with cellulose derivahas for its obiectfto pro amount-cf cellulose esterenteringthe solution nary alcohol group. An example of such is what I have named meth'yletherof methylene phthalate having the formula:

o o d mo om v Q t (flo-omoom and produced for example by reacting anhydrous sodium phthalate with monochlor methyl ether to produce an ester of. phthalic acid comprising a methoxy methylene glycol group.

The reaction may begexpressed by the formula:

A specificexample, illustrating a. composition contemplated; but without intent' to restrict the same, is given as follows: I a

7 Parts Cellulose acetate v100 A low boiling composite "solvent composed of acetone and 15% methanol 400 Methyl ether of methylene glycol phthalate 50 This composition may be used for any suitable purpose andany suitable pigments maybeadded, ifdesired. The proportions" of the'various ingredients may vary over a wide range, depending almost entirely upon the proportions desired in the finished compositionland the use to which it is to be put. Any suitable solvents may be used,

as is well known :in1the art, either singly or in admixture.

It will be understood that other compounds comprising a methylene ether group may be used as plasticizers having the desirable properties accruingp resuinablyfrom the-methyl or methylene ether groupand among such' may be givenjby way of examples, although not by any means all,

and similarly a plasticizermade by reacting the salt of a dibasic straight' chain {saturated'car glycol" boxylic" with a halogen methyl ether and expressed by the formula:

Broadly, a plasticizer is contemplated resulting from afreaction-inwhich one or more carboxyl hydrogefis of' po'lybasic acids are replaced by methylene ether groups of the type -Cl-I2QR where B may be any alkyl group, --CH3 or -CH2OCI-I3, or any cyclicagroup talicyclic or heterocyclic), for exarripla' afloenzene ring such as:

one. furane group, such as:

H s 1' HrT-C- m c (i -H1 CH2O CI I2OC H2 O CH3, or substituted cyclic-group for' instance:

. PH or a 'rriiiidfialiphati'c-"cyclic' 'gr'oup,"fo'r instance:

saturated orunsaturated. L

for instance in theart in the formul'a of the compound form- 'ing 'th'e 'plasticizeriof this invention so long as it v by an alkyl group.

\ ylene group.v

It has been found by experiment that films made as herein described are far superior to the compositions with cellulose derivatives heretofore known when made with a plasticizer such as dimethyl phthalate and have shown a 70% greater flexibility when tested on a SchopDer fold test machine, 'for instance. Furtheriia greater amount of the cellulose derivative goes into solution, it has been found.

Various modifications will occur to those skilled comprises a methylene ether group as well as the proportionsandpther ingredients used to make --c'ompo's'itions"with cellulose derivatives, and no limitation is intended by the phraseology of the foregoing-descriptiomexcept as indicated in the "appended claims.

What is-claimed is: n

1.''A composition of matter comprising a cellulosepderivative:and -an -'ester= of a=.po1ycarboxylic acid: in which-the hydrogen of :at' leastone ofithe carboxyl groups is replaced'by an alkoxy methylene group. 1

*2. A composition of: matter 'comprisinglia-cellulose derivative and an ester: of a polycarboxylic acid; in -:which the :hydrogens of the carboxyl groups are: replaced by alkoxy methylene groups. 3. A composition ofmattercomprising .a cellulose 'derivative and an ester of an'aromatic 'polycarboxyliciacid in which the hydrogen bf atIIeast' one of the carboxylmgroups isPrepIacedHbyA-an alkoxy m'ethylenagroup.

4. A'composition of matter com-prising acellulose derivative and. an' ester of 'an-aliphatic polycarboxylic'iacid in whichthe hydrogen of at least one' of the 'carboxylgroups isv replaced by an alkoxy methylene' group.

+5.:A composition of matteriicomprising a ceb lulose derivative and an- -ester of an aromatic polycarboxylic 1 acid in 'which the hydro'gens of the carboX-yl groups are-replaced by alkoxy methylene groups. I I

6 A composition *of :matter comprising a cellulose derivative and an ester compound'of=phthalic acid-in which the hydrogen of at lea'st one o't the carboxy1 gr ou s is replaced by an alkoiiymitm ylene group. i

7. A" composition of matter comprisinga 'cellulose derivative and an ester of phthalic-acid in which the hydrogens of the carboxyl groupshave been replaced by alkoxy methylene groups.-

8. A composition ofmatter comprising a cellulo'sederivat-ive and an ester compoundofplithalic acid in which the-hydrogen crane-01: the carboxyl groups isreplaced" by an alkoxymethylene group and the hydrogen-of the other A' composition ofmatter comprising acllulose "derivative and "the methyl ether x'of methylene glycol phthalate. I

10. Acomposition of matter comprising 'cellulose acetate, a low boiling composite solventtherefor and an ester ofa' polycarboxylic acid in which the hydrogen" of ""at least one'j'of the"'=carboxyl groups is replaced by an alkoxy'methylene group.

'11.,IA composition of matter comprising. cellu losev acetate, a'low boiling compositefsolventl and the methyl. etheror methylene. 'glycollphthalate.

1 12. A.composition of matter comprisingia. cellu lose derivative and an: ester of a. polycarboxylic group is-replaced acid in w hichthehydrogen of at least one; of the,

carb oxyl,-,g1roups is replaced-byanalkoxy meth- 13. A composition of matter comprising a celluester of a polycarboxylic acid in which the hydrolose derivative and an ester of a polycarboxylic gen of at least one of the carboxyl groups is v acid in-which the hydrogen of at least one of the, replaced by the radical of a mono ether of methcarboxyl groups is replaced by a methoxy-methylene glycol having the structural formula 5 oxy methylene group. p CH2OR. 5 14. A composition of matter comprising a cellu- LEONARD NICHOLL. lose derivative and as a plasticizer therefor the 

